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WO2017208895A1 - Agent de modification pour résine d'ester de cellulose, composition de résine d'ester de cellulose et film optique - Google Patents

Agent de modification pour résine d'ester de cellulose, composition de résine d'ester de cellulose et film optique Download PDF

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Publication number
WO2017208895A1
WO2017208895A1 PCT/JP2017/019154 JP2017019154W WO2017208895A1 WO 2017208895 A1 WO2017208895 A1 WO 2017208895A1 JP 2017019154 W JP2017019154 W JP 2017019154W WO 2017208895 A1 WO2017208895 A1 WO 2017208895A1
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Prior art keywords
cellulose ester
ester resin
residue
acid
dihydric alcohol
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PCT/JP2017/019154
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English (en)
Japanese (ja)
Inventor
昌之 渡辺
毅 富岡
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Daihachi Chemical Industry Co Ltd
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Daihachi Chemical Industry Co Ltd
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Priority to JP2018520815A priority Critical patent/JP6945863B2/ja
Publication of WO2017208895A1 publication Critical patent/WO2017208895A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/50—Polyesters chemically modified by esterification by monohydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a cellulose ester resin modifier, a cellulose ester resin composition, and an optical film.
  • cellulose ester resins have been used as photographic supports because of their toughness and transparency.
  • Cellulose ester resin is not only highly optically transparent, but also optically isotropic, so in recent years it has been used as an optical material for devices that handle polarized light such as liquid crystal displays. It is used as a support for child protective films, optical compensation films that improve the display viewed from an oblique direction, and the like.
  • the cellulose ester film can sufficiently prevent moisture and other moisture from entering. Since it was not possible, there were problems such as deterioration of the polarizer and separation between the polarizer and the protective film. Therefore, conventionally, a film obtained by adding a plasticizer such as triphenyl phosphate to cellulose ester resin and imparting moisture permeability resistance has been used as a polarizer protective film.
  • Patent Documents 2 to 6 describe a polyester in which a terminal is sealed with an aromatic monocarboxylic acid in a condensate of an aromatic dicarboxylic acid and a low-carbon glycol.
  • Patent Document 3 describes a polyester in which a terminal is sealed with an aliphatic monoalcohol or an aliphatic monocarboxylic acid in a condensate of an aliphatic dicarboxylic acid and a low carbon number glycol.
  • Patent Document 4 describes a polyester in which a terminal is sealed with ether alcohol in a condensate of a polybasic acid containing a specific amount of an aromatic dicarboxylic acid and a polyhydric alcohol.
  • Patent Document 5 describes a polyester that is a condensate of an aromatic dicarboxylic acid and a glycol.
  • Patent Document 6 describes a polyester in which a terminal is sealed with acetic acid or benzoic acid in a condensate of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a glycol having a low carbon number.
  • the main object of the present invention is to provide a modifier that imparts excellent moisture permeability to the cellulose ester resin and does not hinder the transparency inherent in the cellulose ester resin.
  • Another object of the present invention is to provide a cellulose ester resin composition containing the modifier, and an optical cellulose ester resin film excellent in moisture permeability and transparency made from the resin composition. .
  • the present invention relates to the cellulose ester resin modifier, the cellulose ester resin composition, and the optical film described in the following items 1 to 10.
  • Item 1 Following formula (1):
  • a 1 and A 2 are the same or different and are each an aliphatic dicarboxylic acid residue.
  • G 1 represents a dihydric alcohol residue, and the dihydric alcohol residue is an aliphatic dihydric alcohol residue or a combination of an aliphatic dihydric alcohol residue and an aromatic dihydric alcohol residue. is there.
  • M 1 and M 2 are the same or different and each represents an aromatic monoalcohol residue.
  • n is an integer of 1 or more.
  • M 1 and M 2 are phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 1-phenylethanol.
  • Item 3. The cellulose ester resin modifier according to Item 1 or 2, which is a residue of at least one aromatic monoalcohol selected from the group consisting of 2-phenylethanol, 2-benzyloxyethanol and 2-phenoxyethanol .
  • Item 4. The cellulose ester resin modifier according to Item 3, wherein M 1 and M 2 are residues of at least one aromatic monoalcohol selected from the group consisting of 2-benzyloxyethanol and 2-phenoxyethanol. .
  • Item 5. Item 5.
  • Item 9. Item 9.
  • a cellulose ester resin composition comprising the cellulose ester resin modifier according to any one of Items 1 to 8, and a cellulose ester resin.
  • Item 10. Item 10.
  • An optical film comprising the cellulose ester resin composition according to Item 9.
  • the present invention it is possible to provide a modifier that imparts excellent moisture permeability resistance to the cellulose ester resin and does not hinder the transparency inherent in the cellulose ester resin.
  • a modifier that imparts excellent moisture permeability resistance to the cellulose ester resin and does not hinder the transparency inherent in the cellulose ester resin.
  • the cellulose ester resin modifier, cellulose ester resin composition and optical film of the present invention will be described.
  • Cellulose ester resin modifier of the present invention is represented by the following formula (1):
  • a 1 and A 2 are the same or different and are each an aliphatic dicarboxylic acid residue.
  • G 1 represents a dihydric alcohol residue, and the dihydric alcohol residue is an aliphatic dihydric alcohol residue or a combination of an aliphatic dihydric alcohol residue and an aromatic dihydric alcohol residue. is there.
  • M 1 and M 2 are the same or different and each represents an aromatic monoalcohol residue.
  • n is an integer of 1 or more.
  • the ester compound represented by these is included.
  • the ester compound is a reaction product of an aliphatic dicarboxylic acid, a dihydric alcohol, and an aromatic monoalcohol. That is, in the ester compound, carboxylic acids at both ends of a polyester (polymer having a repeating unit based on an aliphatic dicarboxylic acid and a dihydric alcohol) obtained by esterifying an aliphatic dicarboxylic acid and a dihydric alcohol are aromatic. It has a structure sealed with a group monoalcohol.
  • the modifier for cellulose ester resin of the present invention contains the ester compound, the transparency and moisture resistance of an optical film obtained from the cellulose ester resin composition containing the modifier and the cellulose ester resin are remarkably improved. Can be improved.
  • the aliphatic dicarboxylic acid residue refers to the remaining group obtained by removing the hydroxyl group from the two carboxyl groups of the aliphatic dicarboxylic acid.
  • a dihydric alcohol residue means the remaining group remove
  • An aromatic monoalcohol residue means the remaining group remove
  • the aliphatic dicarboxylic acid that forms the aliphatic dicarboxylic acid residue represented by A 1 and A 2 in the above formula (1) by the reaction may be linear or branched and has an alicyclic structure. Also good.
  • the number of carbon atoms in the aliphatic dicarboxylic acid is preferably 2 to 15, more preferably 2 to 10, and particularly preferably 2 to 4.
  • aliphatic dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 3-ethyl-3-methylglutaric acid, azelaic acid, heptane-4, 4-dicarboxylic acid, sebacic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 1,4-cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, maleic acid, fumaric acid and acetylenedicarboxylic acid.
  • aliphatic dicarboxylic acids preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, and fumaric acid, and oxalic acid, malonic acid, and succinic acid are particularly preferable.
  • the aliphatic dicarboxylic acid includes carboxylic acid derivatives such as esterified products, acid chlorides, and acid anhydrides.
  • the said aliphatic dicarboxylic acid can be used individually or can use 2 or more types together.
  • the dihydric alcohol residue represented by G 1 in the above formula (1) includes an aliphatic dihydric alcohol residue. Since the aliphatic dihydric alcohol residue is contained in the modifier, compatibility with the cellulose ester resin is improved, so that the transparency of the resulting film can be maintained.
  • the dihydric alcohol that forms the dihydric alcohol residue represented by G 1 in the above formula (1) by the reaction only aliphatic dihydric alcohols can be used, or aliphatic dihydric alcohols and aromatics. These dihydric alcohols can also be used in combination. Particular preference is given to using only aliphatic dihydric alcohols.
  • the aliphatic dihydric alcohol may be linear or branched, and may have an alicyclic structure.
  • the number of carbon atoms in the aliphatic dihydric alcohol is preferably 2 to 15, more preferably 2 to 6, and particularly preferably 2 to 4.
  • Examples of the aliphatic dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl.
  • aliphatic dihydric alcohols may be used alone or in combination of two or more.
  • the aromatic dihydric alcohol refers to a compound having at least one aromatic ring structure in the molecule and two hydroxyl groups.
  • the hydroxyl group in the compound may be directly bonded to the aromatic ring, or may be bonded to another functional group such as an alkyl group bonded to the aromatic ring.
  • the number of carbon atoms in the aromatic dihydric alcohol is preferably 6 to 25, more preferably 6 to 15, and particularly preferably 6 to 10.
  • aromatic dihydric alcohol examples include hydroquinone, resorcinol, 2,2′-biphenol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 1,3-bis (2- (4-hydroxyphenyl) ) -2-propyl) benzene, 1,4-bis (2- (4-hydroxyphenyl) -2-propyl) , 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,2-benzenedimethanol, 1,4-benzenedimethanol, 1,2-benzenediethanol, 1,4-benz
  • aromatic dihydric alcohols hydroquinone, resorcinol, 2,2′-biphenol, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 1,2-benzenedimethanol, , 4-benzenedimethanol, 1,2-benzenediethanol and 1,4-benzenediethanol, particularly preferably hydroquinone, resorcinol, 1,2-benzenedimethanol, 1,4-benzenedimethanol, 1,2 Benzenediethanol and 1,4-benzenediethanol.
  • aromatic dihydric alcohols may be used alone or in combination of two or more.
  • the dihydric alcohol residue represented by G 1 is a combination of an aliphatic dihydric alcohol residue and an aromatic dihydric alcohol residue
  • the aromatic in the dihydric alcohol residue in the ester compound is preferably 80% or less, more preferably 70% or less, and particularly preferably 60% or less.
  • the molar ratio of the aromatic dihydric alcohol residue is “80% or less” means that the molar ratio is “over 0% and 80% or less”.
  • the lower limit of the molar ratio is preferably 0.01%, more preferably 0.1%, further preferably 1%, and particularly preferably 10%.
  • the aromatic monoalcohol that forms an aromatic monoalcohol residue represented by M 1 and M 2 in the above formula (1) by the reaction has at least one aromatic ring structure in the molecule and has one hydroxyl group.
  • the compound which has. By including an aromatic monoalcohol residue in the modifier, the moisture permeability resistance of the resulting film can be improved.
  • the aromatic monoalcohol acts as a sealing agent for ester compounds.
  • the hydroxyl group in the compound may be directly bonded to the aromatic ring, or may be bonded to another substituent such as an alkyl group bonded to the aromatic ring.
  • a particularly preferred form of the aromatic monoalcohol is one in which a hydroxyl group is bonded to an alkyl group, alkoxy group or alkoxyalkyl group bonded to an aromatic ring, and the most preferable form is bonded to an aromatic ring.
  • a hydroxyl group is bonded to an alkoxy group.
  • the aromatic monoalcohol preferably has 6 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and particularly preferably 8 to 10 carbon atoms.
  • aromatic monoalcohol examples include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,3-dimethylphenol, 2, 4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2-propylphenol, 4-propylphenol, 2,3,5-trimethyl Fragrance in which hydroxyl groups such as phenol, 2,3,6-trimethylphenol, 2,4,6-trimethylphenol, 1-naphthol, 2-naphthol, 2-phenylphenol and 4-phenylphenol are directly bonded to the aromatic ring Group monoalcohol; benzyl alcohol, 2- Tilbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 2,3-dimethylbenzyl alcohol, 2,4-di
  • aromatic monoalcohols preferably phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 4-propylphenol, benzyl Alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethylbenzyl alcohol, 3-ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 4-isopropylbenzyl alcohol, 1-phenylethanol, 2 -Phenylethanol, 3-phenyl-1-propanol, 2-phenylphenol, 4-phenylphenol, 2-benzyloxyethanol and 2-phenoxyethanol, more preferably phenol 2-methylphenol, 3-methylphenol, 4-methylphenol, benzyl alcohol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol, 1-phenylethanol, 2-phenylethanol, 2- Benzyloxyethanol and 2-phenoxyethanol, more preferably benzyl alcohol, 2-methylbenzyl alcohol, 2-
  • aromatic monoalcohols may be used alone or in combination of two or more.
  • N indicates the number of repeating units.
  • n is an integer of 1 or more, usually 1 to 20, preferably 2 to 15, and more preferably 3 to 10. If it is the said range, it is excellent in compatibility with a cellulose-ester resin, and is excellent also in the effect which provides plasticity.
  • the number average molecular weight of the ester compound is preferably 500 to 2500, more preferably 700 to 2000, and particularly preferably 800 to 1800. If the number average molecular weight of the ester compound is in the above range, the cellulose ester resin modifier is excellent in bleed resistance even under high temperature and high humidity, and is less likely to volatilize under high temperature conditions including the film production process. Contamination of process equipment and work environment can be suppressed and improved.
  • the number average molecular weight is a value measured by gel permeation chromatography (GPC) in terms of polystyrene using tetrahydrofuran (THF) as an eluent. Detailed measurement conditions are described in the examples.
  • the acid value of the ester compound is the carboxyl group present at the terminal of the polyester that can be produced when the dihydric alcohol and the aliphatic dicarboxylic acid react with each other, the carboxyl group not sealed by the aromatic monoalcohol. It comes from. Polyester having a carboxyl group at the end, which is included in the cellulose ester resin modifier for imparting excellent moisture resistance to the film and maintaining the stability of the cellulose ester resin modifier itself The content of is preferably as small as possible. Therefore, the most preferable value as the acid value is 0, but even when there is an acid value, the effect of the present invention can be sufficiently exhibited within the range shown below.
  • the upper limit when there is an acid value is preferably 3 mgKOH / g or less, more preferably 1 mgKOH / g or less, and particularly preferably 0.7 mgKOH / g or less.
  • the lower limit is preferably about 0.005 mgKOH / g. *
  • the hydroxyl value of the ester compound is derived from the hydroxyl group present at the end of the polyester that can be produced when the dihydric alcohol and the aliphatic dicarboxylic acid react; derived from the unreacted hydroxyl group of the dihydric alcohol used. Things. Since the hydroxyl group has a strong affinity for water, it is preferable that the hydroxyl group is small in order to maintain the moisture permeability resistance of the resulting film. The most preferable value for the hydroxyl value is 0, but even when the hydroxyl value is present, the effects of the present invention can be sufficiently exhibited within the range shown below.
  • the upper limit when there is a hydroxyl value is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and particularly preferably 15 mgKOH / g or less.
  • the lower limit is preferably about 0.1 mgKOH / g.
  • the ester compound can be obtained by reacting the aliphatic dicarboxylic acid, the dihydric alcohol, and the aromatic monoalcohol. Specifically, the aliphatic dicarboxylic acid, the dihydric alcohol and the aromatic monoalcohol are optionally added in the presence of an esterification catalyst, for example, within a temperature range of 100 to 250 ° C. for 10 to 25 hours.
  • the ester compound can be produced by an esterification reaction by a well-known and conventional method. In addition, conditions, such as temperature of esterification reaction and time, are not specifically limited, It can set suitably.
  • the aliphatic dicarboxylic acid, the dihydric alcohol, and the aromatic monoalcohol those described above can be used.
  • the ratio of each of the above components used in production varies depending on the type of components used, the characteristics of the target plasticizer, the molecular weight, and the like.
  • the aliphatic dicarboxylic acid is used in a ratio of 10 to 80% by mass, the dihydric alcohol 10 to 80% by mass, and the aromatic monoalcohol 1 to 50% by mass.
  • the molar ratio of the aromatic dihydric alcohol in the dihydric alcohol in the ester compound is It adjusts suitably so that it may be 80% or less of range, and the total amount becomes the said range.
  • the resulting ester compound is represented by formula (1) wherein A 1 is an aliphatic dicarboxylic acid residue.
  • G 1 is an aliphatic dihydric alcohol residue (A 1 -G 1 )
  • a 1 is an aliphatic dicarboxylic acid residue
  • G 1 is an aromatic dihydric alcohol residue (A 1 -G 1 ) are randomly bonded.
  • esterification catalyst examples include at least one metal or organometallic compound selected from the group consisting of Groups 2, 3, and 4 of the periodic table.
  • metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium; titanium alkoxides such as titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium oxyacetylacetonate;
  • metal compounds such as tin octoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium.
  • Titanium alkoxides such as titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium oxyacetylacetonate in terms of reactivity, ease of handling, and storage stability of ester compounds obtained by esterification Is preferred.
  • the esterification catalyst is preferably used in an amount of about 0.005 to 0.05 parts by mass based on 100 parts by mass of the total amount of the aliphatic dicarboxylic acid, the dihydric alcohol, and the aromatic monoalcohol.
  • the modifier for cellulose ester resin of the present invention contains the ester compound, and preferably comprises the ester compound.
  • the product obtained by the said manufacturing method is, without refine
  • the ester compound but also other impurities (polyester having a hydroxyl group at the terminal, carboxyl group present at the terminal of the polyester, which can be generated when the above-mentioned dihydric alcohol and aliphatic dicarboxylic acid react with each other) Is not sealed with the monoalcohol), but does not particularly inhibit the action of the modifier.
  • the modifier for cellulose ester resin of the present invention is liquid or solid, although it varies depending on the number average molecular weight and composition of the ester compound constituting it.
  • the cellulose ester resin composition of the present invention is a resin composition containing a cellulose ester resin and the cellulose ester resin modifier.
  • the cellulose ester resin composition of the present invention preferably contains about 3 to 30 parts by mass of the modifier for cellulose ester resin, more preferably about 4 to 25 parts by mass with respect to 100 parts by mass of the cellulose ester resin. It is particularly preferable to contain about 5 to 20 parts by mass. If it is a resin composition of the composition of the said range, the film excellent in transparency and moisture permeability can be created.
  • the cellulose ester resin is a cellulose mixed fatty acid ester (cellulose acylate) mainly composed of cellulose acetate.
  • the cellulose as a raw material for cellulose acylate is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like.
  • the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively.
  • the most common industrial synthesis method of cellulose mixed fatty acid ester is to use cellulose corresponding to fatty acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, valeric acid, etc.) or their acid anhydrides.
  • the cellulose acylate examples include L-20, L-30, L-50, L-70, LT-55 (manufactured by Daicel Corporation), CA-394-60LF39 (manufactured by Eastman Chemical Company). Commercial products such as these can also be used.
  • the cellulose ester resin composition of the present invention may contain other components as long as the effects of the present invention are not hindered.
  • other components include additives other than the above, such as polyester-based modifiers, plasticizers, moisture-proofing agents, retardation developing agents, ultraviolet absorbers, infrared absorbers, inorganic fine particles, and dyes.
  • additives known ones that are usually used can be used.
  • optical film of the present invention is a film containing the cellulose ester resin composition.
  • the optical film of the present invention can be obtained by molding the cellulose ester resin composition into a film.
  • the molding method include a method in which the cellulose ester resin composition is melt-kneaded with an extruder or the like and molded into a film by using a T die or the like. It can also be obtained by molding by a solution casting method in which a resin solution obtained by uniformly dissolving and mixing the cellulose ester resin composition in an organic solvent is cast on a support and dried.
  • the solution casting method since the orientation of the cellulose ester resin in the film during molding can be suppressed, the resulting film substantially exhibits optical isotropy.
  • the film showing optical isotropy can be used as a member for a liquid crystal display or the like as an optical film, and is useful as a polarizing plate protective film or an optical compensation film (for an IPS drive type liquid crystal display).
  • Cellulose ester resin Cellulose acetate (manufactured by Daicel Corporation LT-55)
  • Phosphate ester plasticizer 1 Triphenyl phosphate (TPP)
  • Phosphate ester plasticizer 2 biphenylyl diphenyl phosphate (BDP)
  • Ester compounds A to K ester compounds synthesized in Examples and Comparative Examples described later
  • the gas flowing out was condensed through a rectifying device, divided into water produced by the reaction and other low-boiling components, water was recovered, and other low-boiling components were returned to the flask.
  • the rectifying device is removed, and the toroidal tube, the cooling tube, and the 200 ml eggplant flask are attached to the round bottom flask, and the temperature is raised again to 200 ° C. under normal pressure over 10 hours. The temperature was held for 7 hours. Thereafter, a vacuum apparatus was attached to the round bottom flask and maintained at 180 to 200 ° C. for 2 hours under a reduced pressure of 33 kPa.
  • the water produced by the reaction between the normal temperature rise and the reduced pressure hold was collected in a 200 ml eggplant flask. Thereafter, the pressure was reduced to 3 kPa, and then the temperature was raised to 230 ° C. over 7.5 hours to perform polycondensation. As a result, 658 g of a tan solid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound A was 1200, the acid value was 0.12 mgKOH / g, and the hydroxyl value was 13.8 mgKOH / g.
  • Example 2 Synthesis of ester compound B In a 500 ml glass four-necked round bottom flask equipped with a stirrer, a thermometer, and a rectifying apparatus, 116 g (1.1 mol) of benzyl alcohol as an aromatic monoalcohol, 1, 79 g (0.6 mol) of 4-benzenedimethanol and 87 g (1.1 mol) of 1,2-propanediol, 170 g (1.4 mol) of succinic acid as an aliphatic dicarboxylic acid, and tetra-n-butyl titanate as a catalyst. After charging 06 g, the temperature was raised to 230 ° C. at normal pressure over 9 hours.
  • the gas that flowed out was condensed through a rectifier, divided into water produced by the reaction and others, and water was recovered, and the others were returned to the flask.
  • remove the rectifying device attach the T-shaped tube, the cooling tube, and the 200 ml eggplant flask to the round bottom flask, and again raise the temperature to 230 ° C. at normal pressure over 2 hours, 230 ° C. was held for 30 minutes.
  • a vacuum apparatus was attached to the round bottom flask, and maintained at 160 to 180 ° C. for 2 hours under a reduced pressure of 13.3 kPa.
  • the water produced by the reaction between the normal temperature rise and the reduced pressure hold was collected in a 200 ml eggplant flask. Thereafter, the pressure was reduced to 0.4 kPa, and then the temperature was raised to 180 ° C. over 6.5 hours to perform polycondensation. As a result, 299 g of a yellowish brown transparent highly viscous liquid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound B is 1220, the acid value is 0.20 mgKOH / g, the hydroxyl value is 11.8 mgKOH / g, and the molar ratio of 1,4-benzenedimethanol residue to 1,2-propanediol residue Was 4: 6.
  • the gas flowing out was condensed through a rectifying device, divided into water produced by the reaction and other low-boiling components, water was recovered, and other low-boiling components were returned to the flask.
  • the rectifying apparatus was removed, and the To-tube, the cooling tube, and the 200 ml eggplant flask were attached to the round bottom flask, and the temperature was raised again to 240 ° C. under normal pressure over 3 hours.
  • water produced by the reaction was collected in a 200 ml eggplant flask. Thereafter, a vacuum apparatus was attached to the round bottom flask, and the pressure was reduced to 2.3 kPa, and then the temperature was raised to 180 ° C.
  • Example 4 Synthesis of ester compound I In a 1 L glass four-necked round bottom flask equipped with a stirrer, a thermometer, and a rectifying apparatus, 391 g (2.8 mol) of 2-phenoxyethanol as an aromatic monoalcohol and 2 as a dihydric alcohol -After charging 302 g (3.4 mol) of methyl-1,3-propanediol, 279 g (2.4 mol) of succinic acid as an aliphatic dicarboxylic acid, and 0.07 g of tetra-n-butyl titanate as a catalyst, The temperature was raised to ° C over 3 hours.
  • the gas flowing out was condensed through a rectifying device, divided into water produced by the reaction and other low-boiling components, water was recovered, and other low-boiling components were returned to the flask.
  • the rectification apparatus was removed, and the To-tube, the cooling tube, and the 200 ml eggplant flask were attached to the round bottom flask, and the temperature was raised again to 250 ° C. under normal pressure over 3 hours.
  • water produced by the reaction was collected in a 200 ml eggplant flask.
  • a vacuum apparatus was attached to the round bottom flask, and after depressurizing to 2.3 kPa, the temperature was raised to 180 ° C.
  • Example 5 Synthesis of ester compound J Into a 1 L glass four-necked round bottom flask equipped with a stirrer, a thermometer and a rectifying apparatus, 262 g (1.9 mol) of 2-phenoxyethanol as an aromatic monoalcohol and 1 as a dihydric alcohol , 2-propanediol 247 g (3.3 mol), succinic acid 299 g (2.5 mol) as an aliphatic dicarboxylic acid, and 0.07 g of tetra-n-butyl titanate as a catalyst were added to 245 ° C. for 5 hours under normal pressure. The temperature increased over time.
  • the gas flowing out was condensed through a rectifying device, divided into water produced by the reaction and other low-boiling components, water was recovered, and other low-boiling components were returned to the flask.
  • the rectifying device is removed, and the T-tube, the cooling tube, the 200 ml eggplant flask, and the decompression device are attached to the round bottom flask, and the pressure is reduced to 2.3 kPa and then up to 180 ° C.
  • the temperature was raised over 5 hours to carry out polycondensation. During this time, water produced by the reaction was collected in a 200 ml eggplant flask.
  • the gas that flowed out was condensed through a rectifier, divided into water produced by the reaction and others, and water was recovered, and the others were returned to the flask. Thereafter, the rectifying device was removed, and the To-tube, the cooling tube, the 200 ml eggplant flask, and the decompression device were attached to the round bottom flask, and maintained at 160 to 190 ° C. for 12 hours under a reduced pressure of 13.3 kPa.
  • the water produced by the reaction during decompression was collected in a 200 ml eggplant flask. Thereafter, the pressure was reduced to 0.4 kPa, and then the temperature was raised to 180 ° C. over 4.5 hours to perform polycondensation. As a result, 423 g of a tan solid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound C was 1000, and the acid value was 0.29 mgKOH / g.
  • the gas that flowed out was condensed through a rectifier, divided into water produced by the reaction and others, and water was recovered, and the others were returned to the flask.
  • remove the rectifying device attach the T-shaped tube, the cooling tube, and the 200 ml eggplant flask to the round bottom flask, and again raise the temperature to 230 ° C. at normal pressure over 2 hours, 230 ° C. was held for 16 hours.
  • water produced by the reaction was collected in a 200 ml eggplant flask.
  • a decompression device was attached to the round bottom flask, and the pressure was reduced to 0.4 kPa, and then the temperature was raised to 160 ° C. over 5.5 hours to perform polycondensation. After cooling, the pressure was returned to normal pressure, 177 g (1.7 mol) of acetic anhydride was added, and the temperature was maintained at 120 ° C. for 4 hours. Thereafter, the pressure was reduced to 2 kPa while maintaining 120 ° C., and the low boiling point was recovered. As a result, 727 g of a tan transparent liquid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound D was 1300, the acid value was 0.44 mgKOH / g, the hydroxyl value was 0.24 mgKOH / g, and the molar ratio of adipic acid residue to terephthalic acid residue was 2: 1.
  • the rectifying device was removed, and the T-tube, cooling tube, 200 ml eggplant flask, and decompressor were attached to the round bottom flask, and the pressure was reduced to 0.7 kPa over 15.5 hours. Condensation was performed. After cooling, the pressure was returned to normal pressure, 204 g (2.0 mol) of acetic anhydride was added, and 120 ° C. was maintained for 4 hours. Thereafter, the pressure was reduced to 1.3 kPa while maintaining 120 ° C., and the low boiling point was recovered. As a result, 697 g of a pale yellow transparent liquid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound E was 1400, the acid value was 0.20 mgKOH / g, and the hydroxyl value was 0.10 mgKOH / g or less.
  • the rectification apparatus was removed, and the To-tube, the cooling tube, and the 200 ml eggplant flask were attached to the round bottom flask, and kept at 180 ° C. for 4 hours. Thereafter, a vacuum apparatus was attached to the round bottom flask and maintained at 170 to 180 ° C. for 11 hours under a reduced pressure of 10.6 kPa. During this time, water produced by the reaction was collected in a 200 ml eggplant flask. Thereafter, the pressure was reduced to 0.7 kPa over 11.5 hours, but the temperature was raised to 180 ° C. to perform polycondensation. As a result, 591 g of a colorless transparent liquid whose main component is the following formula was obtained.
  • the number average molecular weight of the ester compound F was 1500, the acid value was 0.36 mgKOH / g, and the hydroxyl value was 108 mgKOH / g.
  • the gas that flowed out was condensed through a rectifier, divided into water produced by the reaction and others, and water was recovered, and the others were returned to the flask. Thereafter, the rectifying device was removed, and the To-tube, the cooling tube, the 200 ml eggplant flask, and the pressure reducing device were attached to the round bottom flask, and maintained at 150 to 160 ° C. for 18 hours under a reduced pressure of 24.0 kPa.
  • the water produced by the reaction during decompression was collected in a 200 ml eggplant flask. Thereafter, polycondensation was performed by raising the temperature to 180 ° C. while reducing the pressure to 0.7 kPa over 8 hours.
  • the molar ratio with the group was 1: 1, and the molar ratio between the succinic acid residue and the terephthalic acid residue was 1: 1.
  • Example 11 5 g of a solution in which 2.14 g of cellulose ester resin and 0.26 g of ester compound A were dissolved in a mixed solvent of 34.0 g of methylene chloride, 4.8 g of methanol and 1.2 g of butanol was weighed in a petri dish having a diameter of 94 mm and covered. Later, the whole petri dish was made fluent. Thereafter, the film was allowed to stand at room temperature overnight and then dried at 50 ° C. for 0.5 hour, and then at 100 ° C. for 1 hour to obtain a film having a thickness of 25 ⁇ m. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Example 12 The same operation as in Example 1 was carried out except that the ester compound B was used in place of the ester compound A to obtain a film having a thickness of 27 ⁇ m.
  • the results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Example 13 A film having a thickness of 26 ⁇ m was obtained in the same manner as in Example 1 except that ester compound H was used instead of ester compound A.
  • the results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Example 14 A film having a thickness of 28 ⁇ m was obtained in the same manner as in Example 1 except that ester compound I was used instead of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Example 15 A film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 1 except that ester compound J was used instead of ester compound A.
  • the results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 11 A film having a thickness of 28 ⁇ m was obtained in the same manner as in Example 1 except that ester compound C was used in place of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 12 A film having a thickness of 26 ⁇ m was obtained in the same manner as in Example 1 except that ester compound D was used instead of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 13 A film having a thickness of 26 ⁇ m was obtained in the same manner as in Example 1 except that ester compound E was used instead of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 14 Except that the ester compound F was used instead of the ester compound A, the same operation as in Example 1 was performed to obtain a film having a thickness of 25 ⁇ m.
  • the results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 15 A film having a thickness of 28 ⁇ m was obtained in the same manner as in Example 1 except that ester compound G was used instead of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 16 A film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 1 except that the phosphate ester plasticizer 1 was used instead of the ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 17 A film having a thickness of 24 ⁇ m was obtained in the same manner as in Example 1 except that the phosphate ester plasticizer 2 was used instead of the ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 18 Except not using the ester compound A, the same operation as Example 1 was performed and the film of thickness 24 micrometers was obtained. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Comparative Example 19 A film having a thickness of 26 ⁇ m was obtained in the same manner as in Example 1 except that ester compound K was used in place of ester compound A. The results of measuring the moisture permeability and transparency of the obtained film by the above methods are shown in Table 1.
  • Films containing ester compounds whose ends are sealed with aromatic monoalcohol as in Examples 11 to 15 and Comparative Example 11 are ester compounds sealed with acetic anhydride as in Comparative Examples 12, 13 and 19, Comparative Examples An ester compound that is not end-capped, such as 14, an ester compound that is end-capped with benzoic acid, as in Comparative Example 15, or a phosphate ester plasticizer that has been conventionally used as in Comparative Examples 16 and 17. It can be seen that the moisture permeability is clearly lower than that of the containing film, and the moisture resistance is improved.
  • the film of Comparative Example 11 containing an ester compound in which the dihydric alcohol is an aromatic dihydric alcohol and the terminal is sealed with an aromatic monoalcohol has low moisture permeability, but transparency (haze value). I know it ’s bad. From these facts, it can be seen that the moisture permeation resistance can be improved while maintaining the transparency of the film by including the ester compound of the composition of the present invention as a modifier.

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  • General Chemical & Material Sciences (AREA)
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Abstract

Le but de la présente invention est de fournir un agent de modification qui confère une excellente imperméabilité à l'humidité à une résine d'ester de cellulose et n'inhibe pas la transparence inhérente de la résine d'ester de cellulose. La présente invention concerne un agent de modification pour résine d'ester de cellulose, ledit agent comprenant un composé ester représenté par la formule (1). Dans la formule (1), A1 et A2 sont identiques ou différents et représentent un résidu acide dicarboxylique aliphatique. G1 représente un résidu alcool dihydrique, le résidu alcool dihydrique étant un résidu alcool dihydrique aliphatique ou une combinaison d'un résidu alcool dihydrique aliphatique et d'un résidu alcool dihydrique aromatique. M1 et M2 sont identiques ou différents et représentent un résidu monoalcool aromatique. L'indice n est un nombre entier de 1 ou plus.
PCT/JP2017/019154 2016-06-02 2017-05-23 Agent de modification pour résine d'ester de cellulose, composition de résine d'ester de cellulose et film optique Ceased WO2017208895A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113423777A (zh) * 2019-02-08 2021-09-21 Dic株式会社 光学材料用树脂组合物、光学薄膜和显示装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020049947A1 (fr) * 2018-09-03 2020-03-12 Dic株式会社 Additif pour résine à base d'ester de cellulose, et composition à base d'ester de cellulose

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4732315B1 (fr) * 1969-12-26 1972-08-18
JPS4732316B1 (fr) * 1969-12-26 1972-08-18
JPH03100018A (ja) * 1989-09-14 1991-04-25 Kanebo Ltd 低吸水性ポリエステル樹脂組成物
JPH05155809A (ja) * 1991-12-05 1993-06-22 Satoru Matsumoto エ−テルエステル末端構造を有するジエステル複合エステル並びにポリエステル
JP2005015587A (ja) * 2003-06-25 2005-01-20 Dainippon Ink & Chem Inc 可塑剤、それを含む（メタ）アクリル系樹脂ペースト、及び成形物
JP2009046531A (ja) * 2007-08-14 2009-03-05 Dic Corp セルロースエステル樹脂用改質剤、それを用いたセルロースエステル光学フィルム、及び偏光板用保護フィルム
JP2009155455A (ja) * 2007-12-26 2009-07-16 Fujifilm Corp セルロースエステルフィルム、それを用いた位相差フィルム、偏光板、および液晶表示装置
WO2014115709A1 (fr) * 2013-01-25 2014-07-31 Dic株式会社 Composition d'agent modificateur à base de polyester pour résine d'ester de cellulose, film optique à base d'ester de cellulose, et film protecteur pour plaque polarisante
JP2015007015A (ja) * 2013-06-26 2015-01-15 株式会社Adeka ポリエステル系可塑剤およびセルロース系樹脂組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4732315B1 (fr) * 1969-12-26 1972-08-18
JPS4732316B1 (fr) * 1969-12-26 1972-08-18
JPH03100018A (ja) * 1989-09-14 1991-04-25 Kanebo Ltd 低吸水性ポリエステル樹脂組成物
JPH05155809A (ja) * 1991-12-05 1993-06-22 Satoru Matsumoto エ−テルエステル末端構造を有するジエステル複合エステル並びにポリエステル
JP2005015587A (ja) * 2003-06-25 2005-01-20 Dainippon Ink & Chem Inc 可塑剤、それを含む（メタ）アクリル系樹脂ペースト、及び成形物
JP2009046531A (ja) * 2007-08-14 2009-03-05 Dic Corp セルロースエステル樹脂用改質剤、それを用いたセルロースエステル光学フィルム、及び偏光板用保護フィルム
JP2009155455A (ja) * 2007-12-26 2009-07-16 Fujifilm Corp セルロースエステルフィルム、それを用いた位相差フィルム、偏光板、および液晶表示装置
WO2014115709A1 (fr) * 2013-01-25 2014-07-31 Dic株式会社 Composition d'agent modificateur à base de polyester pour résine d'ester de cellulose, film optique à base d'ester de cellulose, et film protecteur pour plaque polarisante
JP2015007015A (ja) * 2013-06-26 2015-01-15 株式会社Adeka ポリエステル系可塑剤およびセルロース系樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113423777A (zh) * 2019-02-08 2021-09-21 Dic株式会社 光学材料用树脂组合物、光学薄膜和显示装置

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